CN102011010A - Method for totally extracting vanadium, gallium and scandium by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium - Google Patents
Method for totally extracting vanadium, gallium and scandium by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium Download PDFInfo
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- CN102011010A CN102011010A CN2009100638331A CN200910063833A CN102011010A CN 102011010 A CN102011010 A CN 102011010A CN 2009100638331 A CN2009100638331 A CN 2009100638331A CN 200910063833 A CN200910063833 A CN 200910063833A CN 102011010 A CN102011010 A CN 102011010A
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Abstract
The invention relates to a method for extracting, separating and recovering vanadium, gallium and scandium in pickle liquor by adopting a total extracting method and using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium, comprising the following steps of: mixing and stirring titanium dioxide hydrolysis waste acid and steel slag containing vanadium to obtain leaching pulp; performing solid-liquid separation for the leaching pulp, totally extracting vanadium, gallium and scandium in filtered liquor with five-category return flow, then back-extracting vanadium and gallium with five-category return flow, neutralizing with ammonium bicarbonate or ammonia water, warning up, precipitating vanadium to obtain ammonium polyvanadate, repeatedly back-extracting and precipitating vanadium for precipitating-vanadium mother liquor, and then recovering gallium; and when a back-extracting vanadium and gallium organic phase is repeatedly totally extracted and back-extracted till the content of scandium in the back-extracting vanadium and gallium organic phase is 50-1000mg, recovering scandium. The invention has the beneficial effects that waste is treated with waste, namely vanadium, gallium and scandium are recovered by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium, and the sulfuric acid cost is saved; the method has great social and economic benefits and low production cost for producing gallium and scandium; without roasting, no waste gas is produced, and three wastes can be discharged with corresponding standards.
Description
Technical field
The invention belongs to the wet chemistry field of metallurgy, relate to a kind of concretely with titanium dioxide hydrolysis spent acid leaching v-bearing steel slag take the to come together full method of vanadium, gallium and scandium in the immersion liquid of method extracting and separating recovered acid.
Background technology
Climb steel in steelmaking process, annual more than 30 ten thousand tons of the v-bearing steel slags that produce, this slag contains vanadium 1.007-2.040%, gallium 30-70 gram/ton, scandium 6-30 gram/ton, calcium oxide content are used the acid leaching process vanadium extraction up to 34-45%, and the sulfuric acid consumption is up to the 480-620kg/ ton.The production cost height, infeasible economically.Chengdu Univ. of Science ﹠ Technology proposes sodium roasting-carbonating leaching vanadium extraction at this slag vanadium extraction, and because of this processing condition harshness, the material consumption amount is big, and vanadium recovery is low, and gallium and scandium are difficult to reclaim, and production cost is high-leveled and difficult with suitability for industrialized production.At present this v-bearing steel slag send the cement mill to do cement stopping composition and one one except that a part to return the sintering.Major part is all piled the state of abandoning in heaps in the slag field of abandoning.
Panzhihua Region has how tame titanium powder plant, produces per year to contain ten thousand tons of mass percent sulfuric acid 18-25% titanium dioxide hydrolysis spent acid 120-150, and this spent acid contains vanadium 0.4-0.6g/L, gallium 0.2-3mg/L, scandium 1-6mg/L, all producers all adopt and add the processing of lime neutralisation, year processing costs nearly hundred million at present.
At present, the prior art titanium dioxide hydrolysis spent acid also of no use leaching v-bearing steel slag technology of vanadium, gallium and scandium in the immersion liquid of method extracting and separating recovered acid of taking to come together entirely.
Summary of the invention
Problem to be solved by this invention is to provide a kind of at v-bearing steel slag at above-mentioned prior art, utilize the titanium dioxide hydrolysis spent acid to leach this v-bearing steel slag, carry out the method for Separation and Recovery with vanadium, gallium and scandium in the full collection method extraction acidleach, vanadium contained in the titanium dioxide hydrolysis spent acid, gallium, scandium can be comprehensively reclaimed in this method treatment of wastes with processes of wastes against one another.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: a kind of method with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium is characterized in that including the next coming in order step:
1) the titanium dioxide hydrolysis spent acid is mixed stirring with v-bearing steel slag, control leaching endpoint pH 2.0-2.5, and dilution to obtain solid-to-liquid ratio be 1: the leaching ore pulp of 4-10;
2) the step 1) gained is leached ore pulp through the vacuum filtration solid-liquid separation, controlled filter liquid (being water) pH value 2.0-2.2, with the agent of P204-TBP-kerosene extraction as organic phase, wherein compare by volume: organic phase: water=1: 4-25, the Pyatyi adverse current extracts vanadium, gallium and the scandium in the filtered liquid entirely, obtains containing the surplus liquid after vanadium, gallium and scandium load organic phases and the extraction;
3) with step 2) obtain contain vanadium, gallium and scandium load organic phases, with concentration of volume percent is that the 2-20% dilute sulphuric acid is as water, wherein compare by volume: organic phase: water=4-10: 1, the Pyatyi countercurrent reextraction is got vanadium and gallium, obtains back extraction vanadium gallium water and back extraction vanadium gallium organic phase;
4) the back extraction vanadium gallium water that step 3) is obtained is neutralized to pH value 2.0-2.3 with carbon ammonium or ammoniacal liquor, is warming up to 90 degree, soaking time 1 hour, and precipitation gets ammonium poly-vanadate and deposition vanadium mother liquid, and ammonium poly-vanadate obtains Vanadium Pentoxide in FLAKES through calcination;
5) adding sulfuric acid to sulfuric acid volumetric concentration in the deposition vanadium mother liquid that step 4) obtains is 2-20%, as water, and repeating step 3) strip and step 4) precipitation step, carry out the recovery of gallium again;
6) the back extraction vanadium gallium organic phase repeating step 2 that step 3) is obtained) full extraction and step 3) strip stage during scandium content 50-1000mg/L, are carried out the recovery of scandium to back extraction vanadium gallium organic phase.
Press such scheme, the described v-bearing steel slag of step 1) is v-bearing steel slag, vanadium slag and the tailings in vanadium extraction of Panzhihua Inon ﹠ Steel (Group) Co., horse steel group or Chengde steel mill.
Press such scheme, the described leaching endpoint pH of step 1) 2.0-2.2.
Press such scheme, the described v-bearing steel slag of step 1) is that ball milling to mistake-100 order accounts for 70-90%.
Press such scheme, step 2) surplus liquid after the extraction adds lime and is neutralized to pH value 7-8 after-filtration, and filtered liquid is used for the step 1) leaching with titanium dioxide hydrolysis spent acid adjust pH to 2.0-2.2 and dilutes usefulness.
Press such scheme, step 2) described extractant formulation is in volume percent P20410-50%, TBP 2%-50%, kerosene 0-80%.
Press such scheme, the recovery of the described gallium of step 5) is when in the deposition vanadium mother liquid during gallium content 50-2000mg/L, deposition vanadium mother liquid is neutralized to the hydrolysis of pH value 6-7 gallium, filter, filter residue dissolution of sodium hydroxide liquid making, gallium content 5-15g/L in the control alkali lye, sodium hydroxide 150-200g/L, be cathode-anode plate again with the stainless-steel sheet, current density 500-2000A/m
3, groove is pressed 3-4V, electrolysis temperature 40-60 degree electrolysis gallium.
Press such scheme, gallium content 200-2000mg/L in the preferred deposition vanadium mother liquid.
Press such scheme, the recovery of the described scandium of step 6) is to be that 5-15% sodium hydroxide and concentration of volume percent obtain back extraction scandium water and back extraction scandium organic phase for 5-15% ethanol mixing back extraction scandium with back extraction vanadium gallium organic phase concentration of volume percent, back extraction scandium water after filtration, get thick scandium hydroxide, thick scandium hydroxide dissolving with hydrochloric acid, add the heavy scandium of oxalic acid and get the oxalic acid scandium, the oxalic acid scandium gets scandium oxide through 1200 ℃ of calcinations, and back extraction scandium organic phase concentration of volume percent is that the sulfuric acid acidation of 2-5% returns step 2) extraction worker system.
Press such scheme, scandium content 200-1000mg/L in the preferred back extraction vanadium gallium organic phase.
For example: the vanadium high calcium slag that contains with Panzhihua Inon ﹠ Steel's STEELMAKING PRODUCTION is a raw material, hydrolysis spent acid with the how tame titanium powder plant of Panzhihua Region is a leaching agent, control leaching endpoint pH is to 2.0-2.2, with being diluted to solid-to-liquid ratio 1: 4-10 (volume ratio) with tail water among the pH2.0-2.2, solid-liquid separation after filtration, filtered liquid is an organic extractant with 25%P204+2%TBP+73% kerosene (volume percent), (organic phase: water) 1: 4-25 (volume ratio) is compared in control, the full extracting vanadium of Pyatyi adverse current, gallium, scandium, contain vanadium, gallium and scandium load organic phases are compared: (organic phase: water) 4: 1 (volume ratio) back extraction vanadium with 5-20% (volume percent) dilute sulphuric acid Pyatyi adverse current, gallium.Back extraction vanadium, gallium organic phase obtain back extraction scandium water and back extraction scandium organic phase with 5-15% sodium hydroxide+5-15% ethanol (volume percent) back extraction scandium.
Back extraction vanadium gallium water feeds steam and heats to 90 ℃ with carbon ammonium adjust pH to 2.0, is incubated 1 hour, is settled out red ammonium poly-vanadate, and deposition vanadium mother liquid continues adjust pH to the 6-7 hydrolysis, is settled out the gallium concentrate, gets gallium by the electrolysis of the molten liquid making technology of alkali.
It is rough that back extraction scandium water gets scandium after filtration, and reclaim technology by scandium and add dissolving with hydrochloric acid, the refining scandium oxide product that reclaims of the heavy scandium of oxalic acid, back extraction scandium organic phase is returned with the acidifying of 2-5% dilute sulphuric acid and is extracted worker system.
Major technique characteristics of the present invention are:
1) utilize the titanium dioxide hydrolysis spent acid of the how tame titanium powder plant of Panzhihua Region to leach v-bearing steel slag, vanadium slag and tailings in vanadium extraction or the similar material of Panzhihua Inon ﹠ Steel (Group) Co., horse steel group or Chengde steel mill;
2) extract vanadium, gallium and scandium in the pickling liquor with 10-50%P204+2%-50%TBP+0-80% kerosene entirely as extraction agent;
3) extract load organic phases entirely with dilute sulphuric acid reextraction vanadium and gallium, the gallium water is that deposition vanadium mother liquid is enriched to gallium content 200-2000mg/L through the circulation back extraction, in the hydro-oxidation sodium and reclaim gallium;
4) back extraction vanadium gallium organic phase reclaims scandium with sodium hydroxide+ethanol reextraction when the cycling extraction scandium is enriched to 200-1000mg/L.
Beneficial effect of the present invention is:
(1) the present invention is the treatment of wastes with processes of wastes against one another, promptly reclaims vanadium, gallium and scandium with titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, saves the sulfuric acid cost, makes on this process economics worthwhile feasible.Handle spent acid with containing a large amount of calcium oxide replacing limes in the v-bearing steel slag, the processing cost of having saved the titanium dioxide hydrolysis spent acid has great social benefit and economic benefit;
(2) with the disposable full extracting vanadium of P204+TBP+ kerosene, gallium, scandium, vanadium, gallium, scandium in the not only recyclable v-bearing steel slag, and can comprehensively reclaim vanadium contained in the titanium dioxide hydrolysis spent acid, gallium, scandium, production cost is low, need only 4.5-5 ten thousand yuan by smart vanadium production cost per ton, the production cost of subsequent production gallium, scandium is extremely low;
(3) not roasting of the present invention does not have the waste gas generation, and process water tail water is neutralized to pH value 7-8 filtration through adding lime, and filtered liquid is used for leaching process dilution usefulness, non-wastewater discharge with titanium dioxide hydrolysis spent acid adjust pH 2.0-2.5; Acid leaching residue can advance the stacking of mine tailing storehouse and also can be used as the raw material of firing the loam mould common brick through adding the general waste stacking standard that the lime neutralization meets national regulation, or the stopping composition in cement mill, but three wastes qualified discharge can not cause the secondary pollution source.
Embodiment
The present invention will be further described in detail below in conjunction with embodiment, but embodiment can not be construed as limiting the invention.
The titanium dioxide hydrolysis spent acid (dense the crossing of its sulfuric acid do not limit) that adds its volume 2/3rds in pickling tank evenly slowly adds in its pickling tank the v-bearing steel slag that ball milling to mistake-100 order accounts for 70-90%, the limit edged with air or mechanical stirring to terminal the pH value to 2.0-2.5, with the tail water of pH2.0-2.2 or in and tail water (with titanium dioxide hydrolysis spent acid adjust pH 2.0-2.2) be diluted to solid-to-liquid ratio 1: 4-10, through pressure filter or the true filter filtration washing of belt, tailings adds lime and neutralizes into the mine tailing storehouse.
Filtered wash solution, control pH value 2.0-2.2, through box or centrifugal extractor extraction, compare: organic phase: water=1: 4-25, the organic phase proportioning is a volume percent 25%P204+2%TBP+73% kerosene, the full extracting vanadium of Pyatyi adverse current, gallium and scandium obtain containing the surplus liquid after vanadium, gallium and scandium load organic phases and the extraction.Surplus liquid after the extraction adds lime and is neutralized to pH value 7-8 after-filtration, and filter residue and mine tailing are integrated with the mine tailing storehouse.Filtered liquid returns aforementioned leaching process dilution with titanium dioxide hydrolysis spent acid adjust pH 2.0-2.2 and uses.
Contain vanadium, gallium and scandium load organic phases with volumetric concentration 2.0-20% dilute sulphuric acid, compare: organic phase: water=4: 1 Pyatyi countercurrent reextraction vanadium, gallium, back extraction vanadium gallium water and back extraction vanadium gallium organic phase.Back extraction vanadium gallium water carbon ammonium adjust pH 2.0-2.3, by volume concentration is added the ammonium chloride of 2-5%, heats to 90 ℃ of insulations precipitation in 1 hour with steam.Repeating step strip and the precipitation step when in the deposition vanadium mother liquid during gallium content 50-2000mg/L, the deposition vanadium mother liquid adjust pH is to 6-7, the gallium hydrolysed filtrate, filter residue dissolution of sodium hydroxide liquid making, gallium content 5-15g/L in the control alkali lye, sodium hydroxide 150-200g/L is cathode-anode plate again with the stainless-steel sheet, current density 500-2000A/m
3, groove is pressed 3-4V, electrolysis temperature 40-60 degree electrolysis gallium.Back extraction vanadium gallium organic phase repeats full extraction and strip stage to back extraction vanadium gallium organic phase during scandium content 50-1000mg/L, use volumetric concentration 5-15% sodium hydroxide+volumetric concentration 5-15% ethanol again, compare: organic phase: water=4: 1 one-level back extraction scandiums, getting back extraction scandium aqueous phase precipitation thing filters, get thick scandium hydroxide, thick scandium hydroxide dissolving with hydrochloric acid, add the heavy scandium of oxalic acid and get the oxalic acid scandium, the oxalic acid scandium gets scandium oxide through 1200 ℃ of calcinations, back extraction scandium organic phase concentration of volume percent is that the sulfuric acid acidation of 2-5% returns step 2) extraction worker system, filtrate is mended sodium hydroxide and ethanol recycles, and extraction worker system is returned in the acidifying of the organic addition volumetric concentration of back extraction scandium 2-5% dilute sulphuric acid.
Embodiment 1:
(1) earlier at 45M
3Add 28 tons in titanium dioxide hydrolysis spent acid, the complete sour volume percent 38.79% of this titanium dioxide hydrolysis spent acid, free acid 25.93%, ferrous 50.60g/L, ferric iron 0.46g/L, gallium 1.91g/L, scandium 2.28g/L in the pickling tank of stainless steel welding.To contain the vanadium mass percent and contain vanadium 1.061%, contain gallium 34.5g/ ton, the v-bearing steel slag (Panzhihua Inon ﹠ Steel (Group) Co.) of scandium 19.8g/ ton is delivered in the pickling tank that adds the titanium dioxide hydrolysis spent acid through the ball milling limit, v-bearing steel slag limit that ball milling mistake-100 order accounts for mass percent 75.35% with rotary conveyor, the limit edged bleaches with air pump pneumatic blending to v-bearing steel slag, and the pH value is to stop to feed in raw material in 2.01 o'clock.Use 14.5 tons of v-bearing steel slags altogether at every turn, v-bearing steel slag per ton consumes 1.93 tons in titanium dioxide hydrolysis spent acid, 5 batches of co-processing, handle 72.5 tons of v-bearing steel slags, consume 140 tons in spent acid, and with among the pH2.1 and tail water dilution to obtain solid-to-liquid ratio be 1: 8 leaching ore pulp, gained leaching ore pulp belt vacuum filter filtration washing.
(2) get filtered liquid (as full aqueous phase extracted) 290M
3, it contains vanadium 2.19g/L, contains gallium 8.0g/M
3, scandium 3.6g/M
3, pH value 2.19, and with thiosulfuric acid sodium reduction ferric iron.
CTL350-N centrifugal extractor with the production of Hefei work of nature Science and Technology Ltd. carries out the separate unit five grades extraction, and every grade of extraction is once stripped once, and strip liquor recycles to be enriched to vanadiumcontent and reclaims vanadium more than the 30g/L again.With 25%P204+2%TBP+73% kerosene (volume percent) is organic phase, and by volume is compared: organic phase: water=1: 4, with 2200 rev/mins of Frequency Converter Control centrifugal extractor rotating speeds, mix flux 4.5M
3/ h, the Pyatyi adverse current extracts vanadium, gallium and the scandium in the filtered liquid entirely, obtains containing the surplus liquid after vanadium, gallium and scandium load organic phases and the extraction, and the surplus liquid after the extraction contains vanadium 0.09g/L, vanadium percentage extraction 95.89%, gallium 1.93g/M
3, gallium percentage extraction 75.88%, scandium 0.92g/M
3, scandium percentage extraction 74.44%, the surplus liquid after the extraction adds lime and is neutralized to pH value 8 after-filtration, and filtered liquid is used for abovementioned steps (1) leaching dilution with titanium dioxide hydrolysis spent acid adjust pH to 2.1 and uses.
(3) contain vanadium, gallium and scandium load organic phases, with the dilute sulphuric acid of volume percent 15.2%, by volume is compared: organic phase: water=4: 1, Pyatyi countercurrent reextraction vanadium, gallium on unit on the same stage, get back extraction vanadium gallium water, back extraction vanadium gallium water contains vanadium 35.2g/L, gallium 25.6g/M
3, scandium 0.3g/M
3, back extraction vanadium gallium organic phase is returned extraction and is used.
Back extraction vanadium gallium water is with agricultural carbon ammonium adjust pH to 2.0, adding industrial ammonium chloride 50kg. feeding steam by every cubic metre of back extraction vanadium gallium water heats to 90 ℃ of insulations 1 hour, be settled out red ammonium poly-vanadate and deposition vanadium mother liquid, dry with centrigugal swing dryer, altogether contain vanadium mass percent 64.50% ammonium poly-vanadate 862.7kg.Vanadium total yield 72.34% takes off 500 ℃ of calcinations of ammonium with red ammonium poly-vanadate through 250 ℃ and got orange red Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES mass percent 98.43% in 1 hour.
Adding sulfuric acid to sulfuric acid volumetric concentration in the deposition vanadium mother liquid is 14.5%, as water, through aforementioned reextraction and the precipitation enrichment of circulating, when to gallium content 250mg/L, be neutralized to pH value 6-7 gallium hydrolysed filtrate, filter residue dissolution of sodium hydroxide liquid making, obtain gallium content 5.2g/L in the alkali lye, sodium hydroxide 186g/L is a cathode-anode plate with the stainless-steel sheet, current density 1200A/m
3, groove is pressed 3V, electrolysis temperature 50 degree electrolysis galliums; Altogether gallium 2300g, gallium total yield 65.35%.
Scandium in the back extraction vanadium gallium organic phase (contains scandium 10.4g/M in the organic phase
3) through aforementioned full extraction and the reextraction enrichment of circulating.During to scandium content 220mg/L, back extraction vanadium gallium organic phase obtains back extraction scandium water and back extraction scandium organic phase with volume percent 10% sodium hydroxide+volume percent 5% ethanol back extraction scandium, back extraction scandium water filters, get thick scandium hydroxide, thick scandium hydroxide dissolving with hydrochloric acid, it is refining to add the heavy scandium of oxalic acid, the oxalic acid scandium gets the scandium oxide product through 1200 ℃ of calcinations, altogether scandium oxide 2200g, scandium total yield 66.58%, scandium oxide mass percent 99.5%, back extraction scandium organic phase is returned extraction worker system with 5% (concentration of volume percent) sulfuric acid acidation.
Embodiment 2
(1) earlier at 45M
3Add 28 tons in titanium dioxide hydrolysis spent acid, the complete sour volume percent 38.79% of this titanium dioxide hydrolysis spent acid, free acid 25.93%, ferrous 50.60g/L, ferric iron 0.46g/L, gallium 1.91g/L, scandium 2.28g/L in the pickling tank of stainless steel welding.To contain the vanadium mass percent and contain vanadium 1.061%, contain gallium 34.5g/ ton, the v-bearing steel slag (Panzhihua Inon ﹠ Steel (Group) Co.) of scandium 19.8g/ ton is delivered in the pickling tank that adds the titanium dioxide hydrolysis spent acid through the ball milling limit, v-bearing steel slag limit that ball milling mistake-100 order accounts for mass percent 85.35% with rotary conveyor, the limit edged bleaches with air pump pneumatic blending to v-bearing steel slag, and the pH value is to stop to feed in raw material in 2.15 o'clock.Use 13.2 tons of v-bearing steel slags altogether at every turn, v-bearing steel slag per ton consumes 2.0 tons in titanium dioxide hydrolysis spent acid, 5 batches of co-processing, handle 66.0 tons of v-bearing steel slags, consume 132 tons in spent acid, and with among the pH2.1 and tail water dilution to obtain solid-to-liquid ratio be 1: 8 leaching ore pulp, gained leaching ore pulp belt vacuum filter filtration washing.
(2) get filtered liquid 290M
3, it contains vanadium 2.21g/L, contains gallium 8.1g/M
3, scandium 3.7g/M
3, pH value 2.08, and with thiosulfuric acid sodium reduction ferric iron.
CTL350-N centrifugal extractor with the production of Hefei work of nature Science and Technology Ltd. carries out the separate unit five grades extraction, and every grade of extraction is once stripped once, and strip liquor recycles to be enriched to vanadiumcontent and reclaims vanadium more than the 30g/L again.With 50%P204+50%TBP (volume percent) is organic phase, and by volume is compared: organic phase: water=1: 15, with 2200 rev/mins of Frequency Converter Control centrifugal extractor rotating speeds, mix flux 4.5M
3/ h, the Pyatyi adverse current extracts vanadium, gallium and the scandium in the filtered liquid entirely, obtains containing the surplus liquid after vanadium, gallium and scandium load organic phases and the extraction, and the surplus liquid after the extraction contains vanadium 0.07g/L, vanadium percentage extraction 94.85%, gallium 1.90g/M
3, gallium percentage extraction 75.85%, scandium 0.89g/M
3, scandium percentage extraction 73.44%, the surplus liquid after the extraction adds lime and is neutralized to pH value 8 after-filtration, and filtered liquid is used for abovementioned steps (1) leaching dilution with titanium dioxide hydrolysis spent acid adjust pH to 2.1 and uses.
(3) contain vanadium, gallium and scandium load organic phases, with the dilute sulphuric acid of volume percent 4.2%, by volume is compared: organic phase: water=8: 1, Pyatyi countercurrent reextraction vanadium, gallium on unit on the same stage, get back extraction vanadium gallium water, back extraction vanadium gallium water contains vanadium 33.2g/L, gallium 22.4g/M
3, scandium 0.2g/M
3, back extraction vanadium gallium organic phase is returned extraction and is used.
Back extraction vanadium gallium water is with agricultural carbon ammonium adjust pH to 2.0, adding industrial ammonium chloride 50kg. feeding steam by every cubic metre of back extraction vanadium gallium water heats to 90 ℃ of insulations 1 hour, be settled out red ammonium poly-vanadate and deposition vanadium mother liquid, dry with centrigugal swing dryer, altogether contain vanadium mass percent 64.65% ammonium poly-vanadate 850.7kg.Vanadium total yield 72.21% takes off 500 ℃ of calcinations of ammonium with red ammonium poly-vanadate through 250 ℃ and got orange red Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES mass percent 98.60% in 1 hour.
Adding sulfuric acid to sulfuric acid volumetric concentration in the deposition vanadium mother liquid is 14.5%, as water, through aforementioned reextraction and the precipitation enrichment of circulating, when to gallium content 380mg/L, be neutralized to pH value 6-7 gallium hydrolysed filtrate, filter residue dissolution of sodium hydroxide liquid making, obtain gallium content 7.8g/L in the alkali lye, sodium hydroxide 186g/L is a cathode-anode plate with the stainless-steel sheet, current density 1500A/m
3, groove is pressed 3V, electrolysis temperature 40 degree electrolysis galliums; Altogether gallium 2400g, gallium total yield 65.88%.
Scandium in the back extraction vanadium gallium organic phase is through aforementioned full extraction and the reextraction enrichment of circulating.During to scandium content 700mg/L, back extraction vanadium gallium organic phase obtains back extraction scandium water and back extraction scandium organic phase with volume percent 10% sodium hydroxide+volume percent 5% ethanol back extraction scandium, back extraction scandium water filters, get thick scandium hydroxide, thick scandium hydroxide dissolving with hydrochloric acid, it is refining to add the heavy scandium of oxalic acid, the oxalic acid scandium gets the scandium oxide product through 1200 ℃ of calcinations, altogether scandium oxide 2400g, scandium total yield 67.28%, scandium oxide mass percent 99.5%, back extraction scandium organic phase is returned extraction worker system with 5% (concentration of volume percent) sulfuric acid acidation.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (10)
1. method with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium is characterized in that including the next coming in order step:
1) the titanium dioxide hydrolysis spent acid is mixed stirring with v-bearing steel slag, control leaching endpoint pH 2.0-2.5, and dilution to obtain solid-to-liquid ratio be 1: the leaching ore pulp of 4-10;
2) the step 1) gained is leached ore pulp through the vacuum filtration solid-liquid separation, controlled filter liquid pH value 2.0-2.2, with the agent of P204-TBP-kerosene extraction as organic phase, wherein compare by volume: organic phase: water=1: 4-25, the Pyatyi adverse current extracts vanadium, gallium and the scandium in the filtered liquid entirely, obtains containing the surplus liquid after vanadium, gallium and scandium load organic phases and the extraction;
3) with step 2) obtain contain vanadium, gallium and scandium load organic phases, with concentration of volume percent is that the 2-20% dilute sulphuric acid is as water, wherein compare by volume: organic phase: water=4-10: 1, the Pyatyi countercurrent reextraction is got vanadium and gallium, obtains back extraction vanadium gallium water and back extraction vanadium gallium organic phase;
4) the back extraction vanadium gallium water that step 3) is obtained is neutralized to pH value 2.0-2.3 with carbon ammonium or ammoniacal liquor, is warming up to 90 degree, soaking time 1 hour, and precipitation gets ammonium poly-vanadate and deposition vanadium mother liquid, and ammonium poly-vanadate obtains Vanadium Pentoxide in FLAKES through calcination;
5) adding sulfuric acid to sulfuric acid volumetric concentration in the deposition vanadium mother liquid that step 4) obtains is 2-20%, as water, and repeating step 3) strip and step 4) precipitation step, carry out the recovery of gallium again;
6) the back extraction vanadium gallium organic phase repeating step 2 that step 3) is obtained) full extraction and step 3) strip stage during scandium content 50-1000mg/L, are carried out the recovery of scandium to back extraction vanadium gallium organic phase.
2. by the described method of claim 1, it is characterized in that the described v-bearing steel slag of step 1) is v-bearing steel slag, vanadium slag and the tailings in vanadium extraction of Panzhihua Inon ﹠ Steel (Group) Co., horse steel group or Chengde steel mill with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium.
3. by claim 1 or 2 described methods, it is characterized in that the described leaching endpoint pH of step 1) 2.0-2.2 with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium.
4. by claim 1 or 2 described methods, it is characterized in that the described v-bearing steel slag of step 1) is that ball milling to mistake-100 order accounts for 70-90% with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium.
5. by claim 1 or 2 described methods with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium, it is characterized in that step 2) surplus liquid after the extraction adds lime and is neutralized to pH value 7-8 after-filtration, and filtered liquid is used for the step 1) leaching with titanium dioxide hydrolysis spent acid adjust pH to 2.0-2.2 and dilutes usefulness.
6. by claim 1 or 2 described methods, it is characterized in that step 2 with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slags, gallium and scandium) described extractant formulation is with volume percent P20410-50%, TBP 2%-50%, kerosene 0-80%.
7. by claim 1 or 2 described methods with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium, the recovery that it is characterized in that the described gallium of step 5) is when in the deposition vanadium mother liquid during gallium content 50-2000mg/L, deposition vanadium mother liquid is neutralized to the hydrolysis of pH value 6-7 gallium, filter, filter residue dissolution of sodium hydroxide liquid making, gallium content 5-15g/L in the control alkali lye, sodium hydroxide 150-200g/L, be cathode-anode plate again with the stainless-steel sheet, current density 500-2000A/m
3, groove is pressed 3-4V, electrolysis temperature 40-60 degree electrolysis gallium.
8. by the described method of claim 7, it is characterized in that gallium content 200-2000mg/L in the deposition vanadium mother liquid with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium.
9. by claim 1 or the 2 described full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag of using, the method of gallium and scandium, the recovery that it is characterized in that the described scandium of step 6) is to be that 5-15% sodium hydroxide and concentration of volume percent obtain back extraction scandium water and back extraction scandium organic phase for 5-15% ethanol mixing back extraction scandium with back extraction vanadium gallium organic phase concentration of volume percent, back extraction scandium water after filtration, get thick scandium hydroxide, thick scandium hydroxide dissolving with hydrochloric acid, add the heavy scandium of oxalic acid and get the oxalic acid scandium, the oxalic acid scandium gets scandium oxide through 1200 ℃ of calcinations, and back extraction scandium organic phase concentration of volume percent is that the sulfuric acid acidation of 2-5% returns step 2) extraction worker system.
10. by the described method of claim 9, it is characterized in that scandium content 200-1000mg/L in the back extraction vanadium gallium organic phase with the full extracting vanadium of titanium dioxide hydrolysis spent acid leaching v-bearing steel slag, gallium and scandium.
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